CN103852461A - Electrochemical needle point enhanced Raman spectrometry instrument based on scanning probe microscope - Google Patents
Electrochemical needle point enhanced Raman spectrometry instrument based on scanning probe microscope Download PDFInfo
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Abstract
The invention discloses an electrochemical needle point enhanced Raman spectrometry instrument based on a scanning probe microscope. The electrochemical needle point enhanced Raman spectrometry instrument is characterized by comprising a scanning head of the scanning probe microscope, and an atmosphere controlled and matched in-situ spectrum electrolytic cell body which can be matched with a conventional commercial spectrometer laser collection module. The scanning head of the scanning probe microscope adopts a special design, a sample is driven to realize XYZ morphology scanning by adopting piezoelectric ceramics, and the scanning probe is fixed on the electrolytic cell still; the instrument structure is designed based on the lens of undersea glasses, so as to realize maximum excitation and collection efficiency of an electrochemical liquid; although the instrument is based on an inverted mode, the instrument can be used for researching transparent and opaque samples; and oxygen removal seal of the system is realized by adopting an isolation hood, the influence of the oxygen on the system research is avoided, solution volatilization is avoided, and an atmosphere inside a cavity can be controlled through an air inlet/outlet.
Description
Technical field
The present invention relates to a kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy, belong to the micro-and spectrochemistry field of galvanochemistry, scan-probe.
Background technology
Galvanochemistry (Electrochemistry, be called for short EC) all there is close contacting with the development of material, the energy, environment, information science and even life science, traditional electrochemical method is mainly potential electrode electromotive force or electric current, what obtain is the average information of electrode interface macroscopic view, and being difficult to provides the behavior of molecule at surface and interface from the aspect of molecular structure.Ultraviolet, infrared and Raman equimolecular spectral technique are applied to electrochemical work place study, the information such as the relevant electrode surface species mode of action, absorption orientation and the coverage that can directly obtain on molecular level.Wherein Raman spectroscopy, particularly Surface enhanced raman spectroscopy technology have unique advantages such as being subject to little, the high surface sensitivity of the interference of water, have been used to the research of electrochemical process.But because optical microscope system is subject to the restriction of optical diffraction limit, spatial resolution is difficult to break through 200nm conventionally.
Tip-Enhanced Raman Spectroscopy technology (Tip-enhanced Raman spectroscopy is called for short TERS), since report in 2000, has been widely used in every field.It adopts Scanning probe technique that (Au/Ag) needle point with TERS activity is approached to sample (as 1nm), under the exciting of certain wavelength and polarization laser, can produce very strong Electromagnetic enhancement in tip end, improve greatly Raman signal, there is spatial resolution and Single Molecule Detection sensitivity up to 1nm.
If by galvanochemistry and the combination of Tip-Enhanced Raman Spectroscopy technology, realize galvanochemistry Tip-Enhanced Raman Spectroscopy technology (being called for short EC-TERS), can greatly improve electrochemical spatial resolution, the behavior from the layer viewpoint molecule of molecular structure at surface and interface, expands the research field of TERS.But there are a lot of difficulties in the realization of this technology.Wherein the problem of core is that former the design only works in the introducing due to galvanochemistry multilayered medium system (air-glass-water) of object lens under air, cause its light path system to distort, directly cause the optical property of confocal microscope system greatly to decline, observation sample and needle point that cannot high-resolution, be difficult to realize the coupling of effective needle point and laser, therefore excite with collection efficiency all very low.
In order to realize EC-TERS technology, both taken into account the requirement of electro-chemical test to solution layer thickness and solution cleanliness factor, require integrated scanning probe scanning head and spectrum electrolytic cell in limited space simultaneously, reduce to the full extent again the impact on light path performance of solution layer and optical window, improve TERS and excite and collection efficiency.Implement and there is higher difficulty.Also therefore, yet there are no so far the work report of ECTERS.Therefore, invent that a handling are simple, the micro-light path of easy to clean, optical excitation/collection efficiency excellence, the instrument that is applicable to galvanochemistry Tip-Enhanced Raman Spectroscopy in-situ characterization have great importance.
Summary of the invention
The object of the invention is to be difficult to and the problem of electrochemical techniques in conjunction with coupling in order to solve existing pinpoint enhanced Raman technology, design a kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy.The present invention is simple and easy to do in implementation, solve the optical path distortion problem that air object lens exist for electrochemical system, scanning head structure compactness, though making based on transmission mode, Sample Scan mode do not limit the transparency of testing sample, and the assembling of In situ spectroscopic electrolytic cell and clean simple and easy to do.
A galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy, is characterized in that, comprising:
One seal chamber (9), the bottom of this cavity (9) is provided with quartzy window (4), and the below of quartzy window (4) is provided with catoptron (2), the other spectrometer excitation/collection module (1) that is provided with of catoptron (2);
The top of quartz window (4) is provided with object lens (5), and the top of object lens (5) is provided with In situ spectroscopic electrolytic cell (6);
This In situ spectroscopic electrolytic cell (6) bottom is provided with transparent window (19), above transparent window 19, be provided with scan-probe (18), on this In situ spectroscopic electrolytic cell (6), also plug at least one contrast electrode (15) and at least one to electrode (16), this scan-probe (18), contrast electrode (15) and electrode (16) respectively with one electrochemical control device (14) is connected;
The top of this In situ spectroscopic electrolytic cell (6) is provided with movably piezoelectric ceramics fixed mount (11), this piezoelectric ceramics fixed mount (11) is fixed with piezoelectric ceramics (8), the bottom of piezoelectric ceramics (8) is provided with the fixed part of fixed sample, and a step motor (10) is controlled the motion of piezoelectric ceramics fixed mount (11);
It is upper that exciting light focuses on sample (7) by object lens (5) from spectrometer excitation/collection module (1) after catoptron (2) reflection is by quartzy window (4), and raman spectral signal returns and finally enters spectrometer excitation/collection module (1) along original optical path.
In preferred embodiment of the present invention, it is upper motionless that scan-probe (18) is fixed on In situ spectroscopic electrolytic cell (6), and piezoelectric ceramics (8) drives sample (7) to realize the scanning of sample three-dimensional appearance.
In preferred embodiment of the present invention, sample is transparent or opaque sample, conduction or non-conductive sample.
In preferred embodiment of the present invention, this scan-probe (18) electrical connection one preposition amplification (17), this preposition amplification (17) is connected to electrochemical control device (14).
In preferred embodiment of the present invention, seal chamber (9) is provided with at least one air intake opening (12) and at least one exhausr port (13), for controlling atmosphere and the pressure of inside cavity.Avoid the impact of oxygen on architectural study, avoid the volatilization of solution, and the atmosphere of inside cavity can be controlled in enter/gas outlet simultaneously
In preferred embodiment of the present invention, for electrochemical solution system, object lens (5) can adopt high NA(NA value to be greater than 0.5, and for example, NA value is 1.0) hydroscope camera lens, reduces optical distortion and improves system detection sensitivity; For air system, object lens (5) can adopt high NA(NA value to be greater than 0.5, and for example, NA value is 0.7) air object lens.
The galvanochemistry Tip-Enhanced Raman Spectroscopy instrument that the present invention is based on scanning probe microscopy, is characterized in that: the In situ spectroscopic electrolytic cell pond body of scanner head, atmosphere control and the coupling that comprises scanning probe microscopy.The scanner head of scanning probe microscopy adopts ad hoc design, and it adopts piezoelectric ceramics to drive sample to realize the scanning of XYZ pattern, and scan-probe is fixed on electrolytic cell motionless; This apparatus structure designs based on hydroscope camera lens, to realize exciting and collection efficiency of electrochemical solution system maximum; Although it is based on inversion mode, can be for making clear of bright and opaque sample; Adopt seal chamber to realize system deoxygenation sealing, avoid the impact of oxygen on architectural study, avoid the volatilization of solution, and the atmosphere of inside cavity can be controlled in enter/gas outlet simultaneously.
Compared with previous patent, the present invention has following outstanding advantages:
1) compared with routine setting sun formula TERS instrument (object lens NA0.45), the present invention adopts hydroscope camera lens, has effectively avoided galvanochemistry multilayered medium not mate the optical path distortion causing; Hydroscope camera lens NA equals 1.0 simultaneously, and its theoretical collection efficiency is approximately the former 5 times, has greatly improved and has excited and collection efficiency.
2) conventionally the operating distance of hydroscope camera lens is very short, and as 0.1-2.8mm, the present invention adopts special design, allows so fixing scan-probe in narrow space.
3) the present invention adopts Sample Scan, although based on inversion mode, to the not restriction of the sample transparency.
4) the present invention adopts seal chamber to realize deoxygenation sealing, avoids the interference of oxygen to electrochemical system research.Solution evaporation has been avoided in sealing, allows to carry out for a long time the experiment of galvanochemistry Tip-Enhanced Raman Spectroscopy.
5) the spectrometer excitation/collection module using in this patent, can be direct and existing commercial prod is supporting, also can be according to prior art designed, designed.
6) can apply voltage to sample (7) and scan-probe (18) respectively, obtain electrochemical data; Can obtain Tip-Enhanced Raman Spectroscopy data by spectrometer excitation/collection module (1) simultaneously, realize the combination of galvanochemistry and Tip-Enhanced Raman Spectroscopy technology.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Embodiment:
Below in conjunction with accompanying drawing, the present invention will be further described.Fig. 1 is the schematic diagram of the present invention's " a kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy ", number in the figure:
Spectrometer excitation/collection module (1), catoptron (2), O RunddichtringO (3), quartz window (4), object lens (5), In situ spectroscopic electrolytic cell (6), sample (7), piezoelectric ceramics (8), seal chamber (9), step motor (10), piezoelectric ceramics fixed mount (11), air intake opening (12), exhausr port (13), electrochemical control device (14), contrast electrode (15), to electrode (16), preposition amplification (17), scan-probe (18), cover glass (19),
This apparatus structure is as follows:
Comprise a seal chamber (9), the bottom of this cavity (9) is provided with quartzy window (4), and the below of quartzy window (4) is provided with catoptron (2), the other spectrometer excitation/collection module (1) that is provided with of catoptron (2); Between quartz window (4) and seal chamber (9) diapire, be provided with O-ring seal (3) sealing.Air intake opening (12) and at least one exhausr port (13) are one by one established respectively in the top of one seal chamber (9).
The top of quartz window (4) is provided with object lens (5), and the top of object lens (5) is provided with In situ spectroscopic electrolytic cell (6); This In situ spectroscopic electrolytic cell (6) bottom is provided with transparent window (19), this transparent window (19) is made for cover glass, above transparent window (19), be provided with scan-probe (18), on this In situ spectroscopic electrolytic cell (6), also plug at least one contrast electrode (15) and at least one to electrode (16), this scan-probe (18), contrast electrode (15) and electrode (16) respectively with one electrochemical control device (14) is connected; Wherein, this scan-probe (18) is first electrically connected a preposition amplification (17), and this preposition amplification (17) is connected to electrochemical control device (14)
The top of this In situ spectroscopic electrolytic cell (6) is provided with movably piezoelectric ceramics fixed mount (11), this piezoelectric ceramics fixed mount (11) is fixed with piezoelectric ceramics (8), the bottom of piezoelectric ceramics (8) is provided with the fixed part of fixed sample, and a step motor (10) is controlled the motion of piezoelectric ceramics fixed mount (11);
Use of the present invention is as follows:
1, light path calibration
Regulate spectrometer excitation/collection module (1), exciting light is focused on sample (7) by object lens (5) after catoptron (2) reflection is by quartzy window (4) from spectrometer excitation/collection module (1), raman spectral signal returns and finally enters spectrometer excitation/collection module (1) along original optical path, and carry out subsequent optical spectrum light splitting and detection, guarantee that optical quality and signal collection are normal.
2, sample and needle point preparation
Fixing in the jack of sample (7) (as gold (111) monocrystalline after polishing annealing) the insertion piezoelectric ceramics (8) preparing; The active scan-probe of the TERS of end tilts certain angle (as 45 degree) (18) is insulated and sealed, utilize glue to be fixed on electrolytic cell (6), and realize the conductive contact of scan-probe and preposition amplification (17), preposition amplifying signal is further delivered in electrochemical control device (14) and is carried out calculation process.
3, In situ spectroscopic electrolytic cell assembling
After electrolytic cell cleaning, drying, load onto contrast electrode (15) (as silver/silver chloride) and to electrode (16) (as platinum filament), the good cover glass of electrolytic cell bottom package (19), adds galvanochemistry supporting electrolyte.Sample (7), contrast electrode (15) and the conductive lead wire to electrode (16) are all connected to electrochemical control device (14).
4, the aligning of needle point and laser coupling
Exciting light focuses on the upper part of cover glass (19) through object lens (5); Find the position of needle point, and progressively focus on the end of needle point; Utilize step motor (10) that sample (7) is approached to scan-probe (18) until complete inserting needle; Least significant end by laser focusing at needle point, realizes the coupling of needle point and laser.
5, atmosphere control
Cover seal chamber (9), utilize air intake opening (12) and gas outlet (13), can take out the air of inside cavity, can pass into composition, ratio and the pressure of other gas control cavity internal gas compositions, can effectively get rid of the impact of oxygen on electrochemical system research.
6, carry out the test of galvanochemistry Tip-Enhanced Raman Spectroscopy
Utilize piezoelectric ceramics (8) scanning to obtain the surface topography of sample (7), select interested zonule to carry out TERS and adopt spectrum, apply current potential simultaneously and observe the variation relation of sample with current potential, complete the test of galvanochemistry Tip-Enhanced Raman Spectroscopy.
The present invention is not limited to above-mentioned implementation method, can also be the reasonable combination of the technical characterictic described in said method.
Claims (6)
1. the galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy, is characterized in that, comprising:
One seal chamber (9), the bottom of this cavity (9) is provided with quartzy window (4), and the below of quartzy window (4) is provided with catoptron (2), the other spectrometer excitation/collection module (1) that is provided with of catoptron (2);
The top of quartz window (4) is provided with object lens (5), and the top of object lens (5) is provided with In situ spectroscopic electrolytic cell (6);
This In situ spectroscopic electrolytic cell (6) bottom is provided with transparent window (19), above transparent window (19), be provided with scan-probe (18), on this In situ spectroscopic electrolytic cell (6), also plug at least one contrast electrode (15) and at least one to electrode (16), this scan-probe (18), contrast electrode (15) and electrode (16) respectively with one electrochemical control device (14) is connected;
The top of this In situ spectroscopic electrolytic cell (6) is provided with movably piezoelectric ceramics fixed mount (11), this piezoelectric ceramics fixed mount (11) is fixed with piezoelectric ceramics (8), the bottom of piezoelectric ceramics (8) is provided with the fixed part of fixed sample, and a step motor (10) is controlled the motion of piezoelectric ceramics fixed mount (11);
It is upper that exciting light focuses on sample (7) by object lens (5) from spectrometer excitation/collection module (1) after catoptron (2) reflection is by quartzy window (4), and raman spectral signal returns and finally enters spectrometer excitation/collection module (1) along original optical path.
2. a kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy as claimed in claim 1, it is characterized in that: it is upper motionless that scan-probe (18) is fixed on In situ spectroscopic electrolytic cell (6), and piezoelectric ceramics (8) drives sample (7) to realize the scanning of sample three-dimensional appearance.
3. a kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy as claimed in claim 1, is characterized in that: sample is transparent or opaque sample, conduction or non-conductive sample.
4. a kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy as claimed in claim 1, it is characterized in that: this scan-probe (18) electrical connection one preposition amplification (17), this preposition amplification (17) is connected to electrochemical control device (14).
5. a kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy as claimed in claim 1, it is characterized in that: seal chamber (9) is provided with at least one air intake opening (12) and at least one exhausr port (13), for controlling atmosphere and the pressure of inside cavity.
6. a kind of galvanochemistry Tip-Enhanced Raman Spectroscopy instrument based on scanning probe microscopy as claimed in claim 1, is characterized in that: for electrochemical solution system, object lens (5) adopt high NA hydroscope camera lens, reduces optical distortion and improves system detection sensitivity; For air system, object lens (5) adopt high NA air object lens.
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| CN104391137A (en) * | 2014-11-28 | 2015-03-04 | 福州大学 | Novel electro-chemical imaging and temperature imaging synchronizing system for micro-cell |
| CN104931733A (en) * | 2015-06-18 | 2015-09-23 | 厦门大学 | Shell isolation silver nanoparticle tip preparation method |
| CN106198489A (en) * | 2016-08-10 | 2016-12-07 | 苏州华莱德电子科技有限公司 | A kind of molecule knot optical near-field microscopic system and building method thereof |
| CN106813698A (en) * | 2016-12-26 | 2017-06-09 | 中国科学院长春光学精密机械与物理研究所 | The light path sealing mechanism of interface is detected with environmental monitoring and beam quality |
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| CN111982883A (en) * | 2020-09-02 | 2020-11-24 | 鲁东大学 | Graphene/silver hexadecimal array Raman-enhanced substrate and preparation method thereof |
| CN112014308A (en) * | 2020-09-07 | 2020-12-01 | 中国石油大学(华东) | Raman-enhanced electrochemical corrosion cell and control method thereof |
| WO2023000909A1 (en) * | 2021-07-19 | 2023-01-26 | 张玉芝 | Minute-scale high-sensitivity micro-current controlled raman detection apparatus and method |
| WO2024016425A1 (en) * | 2022-07-19 | 2024-01-25 | 厦门大学 | Electrochemical nano infrared spectromicroscope and analysis method |
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| CN104391137B (en) * | 2014-11-28 | 2017-01-25 | 福州大学 | Electro-chemical imaging and temperature imaging synchronizing system for micro-cell and method thereof |
| CN104391137A (en) * | 2014-11-28 | 2015-03-04 | 福州大学 | Novel electro-chemical imaging and temperature imaging synchronizing system for micro-cell |
| CN104931733A (en) * | 2015-06-18 | 2015-09-23 | 厦门大学 | Shell isolation silver nanoparticle tip preparation method |
| CN104931733B (en) * | 2015-06-18 | 2017-12-22 | 厦门大学 | A kind of preparation method of shell isolated silver nanoparticle needle point |
| CN106198489B (en) * | 2016-08-10 | 2019-04-02 | 苏州华莱德电子科技有限公司 | A kind of molecule knot optical near-field microscopic system and its building method |
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| CN106813698A (en) * | 2016-12-26 | 2017-06-09 | 中国科学院长春光学精密机械与物理研究所 | The light path sealing mechanism of interface is detected with environmental monitoring and beam quality |
| CN107727886A (en) * | 2017-10-31 | 2018-02-23 | 北京航空航天大学 | A kind of inversion type high speed Electrochemical Atomic Force Microscopy |
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| CN111982883A (en) * | 2020-09-02 | 2020-11-24 | 鲁东大学 | Graphene/silver hexadecimal array Raman-enhanced substrate and preparation method thereof |
| CN111982883B (en) * | 2020-09-02 | 2023-04-14 | 鲁东大学 | Graphene/silver hexadecimal array Raman-enhanced substrate and preparation method thereof |
| CN112014308A (en) * | 2020-09-07 | 2020-12-01 | 中国石油大学(华东) | Raman-enhanced electrochemical corrosion cell and control method thereof |
| WO2023000909A1 (en) * | 2021-07-19 | 2023-01-26 | 张玉芝 | Minute-scale high-sensitivity micro-current controlled raman detection apparatus and method |
| WO2024016425A1 (en) * | 2022-07-19 | 2024-01-25 | 厦门大学 | Electrochemical nano infrared spectromicroscope and analysis method |
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